Reduction of adsorbed As(V) on nano-TiO₂ by sulfate-reducing bacteria

Reduction of surface-bound arsenate [As(V)] and subsequent release into the aqueous phase contribute to elevated As in groundwater. However, this natural process is not fully understood, especially in the presence of sulfate-reducing bacteria (SRB). Gaining mechanistic insights into solid-As(V)-SRB interactions motivated our molecular level study on the fate of nano-TiO₂ bound As(V) in the presence of Desulfovibrio vulgaris DP4, a strain of SRB, using incubation and in situ ATR-FTIR experiments. The incubation results clearly revealed the reduction of As(V), either adsorbed on nano-TiO₂ or dissolved, in the presence of SRB. In contrast, this As(V) reduction was not observed in abiotic control experiments where sulfide was used as the reductant. Moreover, the reduction was faster for surface-bound As(V) than for dissolved As(V), as evidenced by the appearance of As(III) at 45h and 75h, respectively. ATR-FTIR results provided direct evidence that the surface-bound As(V) was reduced to As(III) on TiO₂ surfaces in the presence of SRB. In addition, the As(V) desorption from nano-TiO₂ was promoted by SRB relative to abiotic sulfide, due to the competition between As(V) and bacterial phosphate groups for TiO₂ surface sites. This competition was corroborated by the ATR-FTIR analysis, which showed inner-sphere surface complex formation by bacterial phosphate groups on TiO₂ surfaces. The results from this study highlight the importance of indirect bacteria-mediated As(V) reduction and release in geochemical systems.